3-Aminophenol derivatives and dyes that contain these compounds while serving to dye keratin fibers

ABSTRACT

The object of the present patent application are 3-aminophenol derivatives of formula (I) or the physiologically compatible, water-soluble salts thereof  
                 
 
     and colorants based on a developer-coupler combination containing these compounds.

[0001] The present invention relates to novel 3-aminophenol derivativessubstituted in the 2-position and to agents for dyeing keratin fibers,particularly human hair, containing these agents.

[0002] Oxidation dyes have attained substantial importance in the fieldof keratin fiber dyeing and particularly hair dyeing. The color isgenerated by reaction of certain developers with certain couplers in thepresence of an appropriate oxidant. The developers used for this purposeare, in particular, 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol,p-aminophenols, 1,4-diaminobenzene and4,5-diamino-1-(2-hydroxyethyl)pyrazole, whereas suitable couplers are,for example, resorcinol, 2-methylresorcinol, 1-naphthol,5-amino-2-methylphenol, m-phenylenediamine,2-amino-4-(2′-hydroxyethyl)amino-anisole,1,3-diamino-4-(2′-hydroxyethoxy)benzene and 2,4-diamino-5-fluorotoluene.

[0003] In addition to being able to produce colors of the desiredintensity, oxidation dyes used for dyeing human hair must meet manyadditional requirements. For example, such dyes must be unobjectionablefrom a toxicological and dermatological standpoint, and the haircolorations obtained must be highly resistant to light, permanentwaving, acids and rubbing. In any case, however, in the absence ofexposure to light, rubbing and chemical agents such colorations mustremain stable for a period of at least 4 to 6 weeks. Moreover, it mustbe possible, by a combination of suitable developers and couplers, toproduce a wide range of different color shades.

[0004] Although many couplers are already known, with the currentlyknown colorants it is not possible to meet the requirements placed on acolorant in every respect. Hence, a need continues to exist for novelcouplers that will meet the aforesaid requirements to an especially highdegree.

[0005] We have now found that certain 3-aminophenol derivatives ofgeneral formula (I) meet the requirements placed on couplers to anespecially high degree and with known developers give intense andunusually light-fast and wash-fast color shades.

[0006] Hence, the object of the present invention are novel3-aminophenol derivatives of formula (I) or physiologically compatible,water-soluble salts thereof,

[0007] wherein

[0008] X₁, X₂, X₃ and X₄ independently of each other denote sulfur,nitrogen, N—R1, oxygen, C—R2, C—R3, C—R4 or C—R5, provided that at leastone and at the most three of the X₁ to X₄ groups denote nitrogen, N—R1,sulfur or oxygen, and if several heteroatoms are present, at the mostone of the X₁ to X₄ groups denotes sulfur, N—R1 or oxygen;

[0009] R1 denotes hydrogen, a C₁-C₈-alkyl group, a phenyl group, a(C₂-C₄)-hydroxyalkyl group or an acetyl group;

[0010] R2, R3, R4 and R5 independently of each other denote hydrogen, ahalogen atom (F, Cl, Br, I), a cyano group, a C₁-C₆-alkyl group, aC₁-C₄-alkoxy group, a C₁-C₄-alkyl thioether group, a mercapto group, anitro group, an amino group, a C₁-C₄-alkylamino group, adi(C₁-C₄)-alkylamino group, a hydroxy-(C₂-C₄)-alkylamino group, adi[hydroxy(C₁-C₄)-alkyl]amino group, a [dihydroxy-(C₃-C₄)-alkyl]aminogroup, a trifluoromethyl group, an acetyl group, a trifluoroacetylgroup, a formyl group, a trimethylsilyl group, a (C₁-C₄)-hydroxyalkylgroup or a (C₂-C₄)-dihydroxyalkyl group, or two adjacent R2 to R5 groupstogether with the remainder of the molecule form a heterocyclic orcarbocyclic, substituted or unsubstituted ring.

[0011] Suitable compounds of formula (I) are, for example:3-amino-2-(3-thienyl)phenol, 3-amino-2-(3-furyl)phenol,3-amino-2-(pyrrol-3-yl)phenol,3-amino-2-(1-methyl-1H-pyrrol-3-yl)phenol,3-amino-2-(1,3-thiazol-2-yl)phenol, 3-amino-2-(1,3-thiazol-5-yl)phenol,3-amino-2-(2-thienyl)phenol, 3-amino-2-(2-furyl)phenol,3-amino-2-(pyrrol-2-yl)phenol,3-amino-2-(1-methyl-1H-pyrrol-2-yl)phenol,3-amino-2-(2-chloro-3-(thienyl)phenol,3-amino-2-(2-methyl-3-thienyl)phenol,3-amino-2-(benzo[b]thiophen-2-yl)phenol,3-amino-2-(5-phenyl-2-thienyl)phenol,3-amino-2-(2-nitro-3-thienyl)phenol,3-amino-2-(2-amino-3-thienyl)phenol,3-amino-2-(2-acetyl-3-thienyl)phenol,3-amino-2-(2-formyl-3-thienyl)phenol,3-amino-2-(4-chloro-3-thienyl)phenol,3-amino-2-(4-methyl-3-thienyl)phenol, 3-amino-(4-nitro-3-thienyl)phenol,3-amino-2-(4-amino-3-thienyl)phenol,3-amino-2-(4-acetyl-3-thienyl)phenol,3-amino-2-(4-formyl-3-thienyl)phenol,3-amino-2-(5-chloro-3-thienyl)phenol,3-amino-2-(5-methyl-3-thienyl)phenol,3-amino-2-(5-phenyl-3-thienyl)phenol,3-amino-2-(5-nitro-3-thienyl)phenol,3-amino-2-(5-acetyl-3-thienyl)phenol,3-amino-2-(5-amino-3-thienyl)phenol,3-amino-2-(5-formyl-3-thienyl)phenol,3-amino-2-(benzo[b]thiophen-3-yl)phenol,3-amino-2-(5-formyl-3-furyl)phenol,3-amino-2-(3-chloro-2-thienyl)phenol,3-amino-2-(3-methyl-2-thienyl)phenol,3-amino-2-(3-nitro-2-thienyl)phenol,3-amino-2-(3-amino-2-thienyl)phenol,3-amino-2-(3-acetyl-2-thienyl)phenol,3-amino-2-(3-formyl-2-thienyl)phenol,3-amino-2-(4-chloro-2-thienyl)phenol,3-amino-2-(4-methyl-2-thienyl)phenol,3-amino-2-(4-nitro-2-thienyl)phenol,3-amino-2-(4-amino-2-thienyl)phenol,3-amino-2-(4-acetyl-2-thienyl)phenol,3-amino-2-(4-formyl-2-thienyl)phenol,3-amino-2-(5-chloro-2-thienyl)phenol,3-amino-2-(5-methyl-2-thienyl)phenol,3-amino-2-(5-nitro-2-thienyl)phenol,3-amino-2-(5-amino-2-thienyl)phenol,3-amino-2-(5-acetyl-2-thienyl)phenol,3-amino-2-(5-formyl-2-thienyl)phenol,3-amino-2-(5-formyl-2-furyl)phenol,3-amino-2-(5-nitro-1,3-thiazol-2-yl)phenol,3-amino-2-(5-amino-1,3-thiazol-2-yl)phenol,3-amino-2-(2-nitro-1,3-thiazol-5-yl)phenol,3-amino-2-(2-amino-1,3-thiazol-5-yl)phenol,3-amino-2-(3,5-dimethylisoxazol-4-yl)phenol,3-amino-2-(3,5-dimethyl-1H-pyrazol-4-yl)phenol and3-amino-2-(5-nitro-4H-1,2,4-triazol-3-yl)phenol as well as thephysiologically compatible, water-soluble salts thereof.

[0012] Preferred compounds of formula (I) are those wherein:

[0013] (i) X₂ denotes sulfur and X₁, X₃ and X₄ denote C—R2, C—R4 andC—R5 or (ii) X₁ denotes sulfur and X₂, X₃ and X₄ denote C—R3, C—R4 andC—R5.

[0014] Particularly preferred are the following compounds of formula(I):

[0015] 3-amino-2-(3-thienyl)phenol, 3-amino-2-(2-thienyl)phenol,3-amino-2-(benzo[b]thiophen-3-yl)phenol and3-amino-2-(5-phenyl-2-thienyl)phenol as well as the physiologicallycompatible, water-soluble salts thereof.

[0016] The compounds of formula (I) can be used as the free bases aswell as in the form of their physiologically compatible salts ofinorganic or organic acids, for example hydrochloric acid, sulfuricacid, phosphoric acid, acetic acid, propionic acid, lactic acid orcitric acid.

[0017] The 3-aminophenol derivatives of formula (I) of the invention canbe prepared by methods of synthesis known from the literature, forexample

[0018] a) by tetrakis(triphenylphosphine)palladium(0)-catalyzed couplingof a halogen-substituted 3-aminophenol of formula (IIa) with a boricacid derivative of formula (IIIa) followed by removal of the protectivegroup needed for the coupling reaction and by reduction of an optionallypresent nitro group;

[0019] or

[0020] b) by tetrakis(triphenylphosphine)palladium(0)-catalyzed couplingof an appropriate substituted 3-aminophenolboric acid derivative offormula (IIb)

[0021] with a halogen-substituted aromatic compound of formula (IIIb)followed by removal of the protective group needed for the couplingreaction and by reduction of an optionally present nitro group;

[0022] the other groups used in formulas (Ia), (IIb), (IIIa) and (IIIb)having the following meaning:

[0023] Ra denotes a protective group as described, for example, in thechapter on “Protective Groups” in Organic Synthesis, chapter 3, WileyInterscience, 1991;

[0024] Rb and Rc independently of each other denote hydrogen or aprotective group as described, for example, in the chapter on“Protective Groups” in Organic Synthesis, chapter 7, Wiley Interscience,1991, or Rb and Rc together with the N-atom form a nitro group;

[0025] Rd denotes hydrogen or the two Rd groups together with the—O—B—O— group form an unsubstituted or substituted five-membered orsix-membered cycloaliphatic ring;

[0026] Hal denotes F, Cl, Br or I; and

[0027] X₁, X₂, X₃ and X₄ have the same meaning as in formula (I).

[0028] The 3-aminophenol derivatives of formula (I) are readilywater-soluble and give colorations of excellent color intensity andcolor stability, particularly in terms of light fastness, wash fastnessand rubbing fastness. Moreover, they have excellent storage stabilityparticularly as constituents of the oxidative colorants described in thefollowing.

[0029] Another object of the present invention is therefore an agent forcoloring keratin fibers, for example wool, furs, feathers or hair andparticularly human hair, said agent being based on a developer-couplercombination and being characterized in that it contains at least one3-aminophenol derivative of formula (I) or a physiologically compatible,water-soluble salt thereof.

[0030] The 3-aminophenol derivatives of formula (I) are present in thecolorant of the invention in a total amount from about 0.005 to 20weight percent, an amount from about 0.01 to 5 weight percent andparticularly from 0.1 to 2.5 weight percent being preferred.

[0031] Preferred developers are 1,4-diaminobenzene (p-phenylenediamine),1,4-diamino-2-methylbenzene (p-toluylenediamine),1,4-diamino-2,6-dimethylbenzene, 1,4-diamino-3,5-diethylbenzene,1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,3-dimethylbenzene,2-chloro-1,4-diaminobenzene, 1,4-diamino-2-(2-thienyl)benzene,1,4-diamino-2-(3-thienyl)benzene, 1,4-diamino-2-(pyridin-3-yl)benzene,2,5-diaminobiphenyl, 1,4-diamino-2-methoxymethylbenzene,1,4-diamino-2-aminomethylbenzene, 1,4-diamino-2-hydroxymethylbenzene,1,4-diamino-2-(2-hydroxyethoxy)benzene,2-[2-(acetylamino)ethoxy]-1,4-diaminobenzene, 4-phenylaminoaniline,4-dimethylaminoaniline, 4-diethylaminoaniline, 4-dipropylaminoaniline,4-[ethyl-(2-hydroxyethyl)amino]aniline,4-[di(2-hydroxyethyl)amino]aniline,4-[di(2-hydroxyethyl)amino]-2-methylaniline,4-[(2-methoxyethyl)amino]aniline, 4-[(3-hydroxypropyl)amino]aniline,4-[(2,3-dihydroxypropyl)amino]aniline,1,4-diamino-2-(1-hydroxyethyl)benzene,1,4-diamino-2-(2-hydroxyethyl)benzene,1,4-diamino-2-(1-methylethyl)benzene,1,3-bis-[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol,1,4-bis-[(4-aminophenyl)amino]butane,1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-aminophenol,4-amino-3-methylphenol, 4-amino-3-(hydroxymethyl)phenol,4-amino-3-fluorophenol, 4-methylaminophenol,4-amino-2-(aminomethyl)phenol, 4-amino-2-(hydroxymethyl)phenol,4-amino-2-fluorophenol, 4-amino-2-[(2-hydroxyethyl)amino]methylphenol,4-amino-2-methylphenol, 4-amino-2-(methoxymethyl)phenol,4-amino-2-(2-hydroxyethyl)phenol, 5-aminosalicylic acid,2,5-diaminopyridine, 2,4,5,6-tetra-aminopyrimidine,2,5,6-triamino-4-(1H)-pyrimidone,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole,4,5-diamino-1-(1-methylethyl)-1H-pyrazole,4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole,1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole,4,5-diamino-1-methyl-1H-pyrazole, 2-aminophenol, 2-amino-6-methylphenol,2-amino-5-methylphenol and 1,2,4-trihydroxybenzene.

[0032] Moreover, besides the compounds of formula (I) the colorant ofthe invention can also contain other known couplers, for exampleN-(3-dimethylaminophenyl)urea, 2,6-diaminopyridine,2-amino-4-[(2-hydroxyethyl)amino]anisole,2,4-diamino-1-fluoro-5-methylbenzene,2,4-diamino-1-methoxy-5-methylbenzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene,2,3-diamino-6-methoxypyridine,3-amino-6-methoxy-2-(methylamino)pyridine,2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)benzene,1,3-diamino-4-(2,3-dihydroxypropoxy)benzene,1,3-diamino-4-(3-hydroxypropoxy)benzene,1,3-diamino-4-(2-methoxyethoxy)benzene,2,4-diamino-1,5-di(2-hydroxyethoxy)benzene,1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene,2,4-diaminophenoxyacetic acid, 3-[di(2-hydroxyethyl)amino]-aniline,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene,5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline,3-[(2-aminoethyl)amino]aniline, 1,3-di(2,4-diaminophenoxy)propane,di(2,4-diaminophenoxy)methane, 1,3-diamino-2,4-dimethoxybenzene,2,6-bis-(2-hydroxyethyl)aminotoluene, 4-hydroxyindole,3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol,5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol,5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol,3-amino-2-chloro-6-methylphenol, 3-aminophenol,2-[(3-hydroxyphenyl)amino]acetamide,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,5-[(2-hydroxyethyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]phenol, 3-[(2-methoxyethyl)amino]phenol,5-amino-2-ethylphenol, 5-amino-2-methoxyphenol,2-(4-amino-2-hydroxyphenoxy)ethanol,5-[(3-hydroxypropyl)amino]-2-methylphenol,3-[(2,3-dihydroxypropyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 5-amino-4-chloro-2-methylphenol,1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 2-methyl-1-naphthol acetate,1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene,2-chloro-1,3-dihydroxybenzene,1,2-dichloro-3,5-dihydroxy-4-methylbenzene,1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline,5-[(2-hydroxyethyl)amino]-1,3-benzodioxole,6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)benzoxazine,6-amino-3,4-dihydro-1,4(2H)benzoxazine, 3-methyl-1-phenyl-5-pyrazolone,5,6-dihydroxyindole, 5,6-dihydroxyindoline, 5-hydroxyindole,6-hydroxyindole, 7-hydroxyindole and 2,3-indolinedione.

[0033] The couplers and developers can be contained in the colorant ofthe invention either individually or in admixture with each other, thetotal amount of couplers and developers in the colorant of the invention(based on the total amount of colorant) being from about 0.005 to 20weight percent, preferably from about 0.01 to 5 weight percent andparticularly from 0.1 to 2.5 weight percent, each.

[0034] The total amount of the developer-coupler combination containedin the colorant described herein is preferably from about 0.01 to 20weight percent, an amount from about 0.02 to 10 weight percent andparticularly from 0.2 to 6 weight percent being especially preferred. Ingeneral, the developers and couplers are used in approximately equimolaramounts. However, it is not disadvantageous if the developers arepresent in a certain excess or deficiency with respect to such anamount.

[0035] Moreover, the colorant of the invention can also contain otherdye components, for example 6-amino-2-methylphenol and2-amino-5-methylphenol as well as common synthetic or natural directdyes, for example vegetable dyes or synthetic direct dyes from the groupof acid or basic dyes (for example the cationic dyes described in WO95/15144 or European Unexamined Patent Application EP 0 850 638),triphenylmethane dyes, aromatic nitro dyes, azo dyes and disperse dyes.The colorants of the invention can contain these dye components in anamount from about 0.1 to 4 weight percent.

[0036] Naturally, the additional couplers and the developers and otherdye components, provided they are bases, can also be used in the form oftheir physiologically compatible salts of organic or inorganic acids,for example hydrochloric acid or sulfuric acid, or—if they containaromatic OH— groups—in the form of salts of bases, for example as alkalimetal phenoxides.

[0037] Moreover, if the colorants are used for dyeing hair, they canalso contain common cosmetic additives, for example antioxidants such asascorbic acid, thioglycolic acid or sodium sulfite, as well as perfumeoils, complexing agents, wetting agents, emulsifiers, thickeners andhair-care agents.

[0038] The colorant of the invention can be formulated, for example, asa solution, particularly an aqueous or aqueous-alcoholic solution. Aparticularly preferred formulation, however, is a cream, gel oremulsion. Such a preparation consists of a mixture of dye components andadditives commonly used for such preparations.

[0039] Common additives to solutions, creams, emulsions or gels are, forexample, solvents such as water, lower aliphatic alcohols, for exampleethanol, propanol or isopropanol, glycerol or glycols such as1,2-propylene glycol; moreover wetting agents or emulsifiers from theclasses of anionic, cationic, amphoteric or nonionic surface-activesubstances such as, for example, the fatty alcohol sulfates, ethoxylatedfatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates,alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols,ethoxylated nonylphenols, fatty alkanolamides and ethoxylated fattyesters, furthermore thickeners such as the higher fatty alcohols,starch, cellulose derivatives, petrolatum, paraffin oil and fatty acids;moreover hair-care agents such as cationic resins, lanolin derivatives,cholesterol, emulsifiers from the classes of anionic, cationic,amphoteric or nonionic surface-active substances such as, for example,the fatty alcohol sulfates, ethoxylated fatty alcohol sulfates,alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts,alkylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols,fatty alkanolamides and ethoxylated fatty esters, furthermore thickenerssuch as the higher fatty alcohols, starch, cellulose derivatives,petrolatum, paraffin oil and fatty acids; moreover hair-care agents suchas cationic resins, lanolin derivatives, cholesterol, pantothenic acidand betaine. The said constituents are used in amounts commonly employedfor such purposes, for example the wetting agents and emulsifiers at aconcentration from about 0.5 to 30 weight percent, the thickeners in anamount from about 0.1 to 30 weight percent and the hair-care agents at aconcentration from about 0.1 to 5 weight percent.

[0040] Depending on the composition, the colorant of the invention canbe weakly acidic, neutral or alkaline. In particular, it has a pH from6.5 to 11.5, the adjustment to a basic value preferably being achievedwith ammonia. However, amino acids and/or organic amines, for examplemonoethanolamine or triethanolamine, or inorganic bases, for examplesodium hydroxide or potassium hydroxide can also be used. For pHadjustment in the acidic range, an inorganic or organic acid, forexample phosphoric acid, acetic acid, citric acid or tartaric acid, canbe used.

[0041] For use in oxidative dyeing of hair, the afore-described colorantis mixed with an oxidant just before use and the resulting mixture isapplied to the hair in an amount sufficient for the hair treatment, ingeneral in an amount from about 60 to 200 grams, depending on thefullness of the hair.

[0042] Suitable oxidants for developing the hair coloration are mainlyhydrogen peroxide or the compounds of addition thereof to urea,melamine, sodium borate or sodium carbonate in the form of a 3 to 12%,preferably 6% aqueous solution. Atmospheric oxygen can also be used. Ifa 6% hydrogen peroxide solution is used as oxidant, the weight ratio ofhair colorant to oxidant is from 5:1 to 1:2 and preferably 1:1. Largeramounts of oxidant are used primarily at higher dye concentrations inthe hair colorant or when more pronounced hair bleaching is wanted atthe same time. The mixture is allowed to act on the hair at 15 to 50° C.for about 10 to 45 minutes, preferably for 30 minutes, after which thehair is rinsed with water and dried. Optionally, following this rinsingthe hair is washed with a shampoo and optionally post-rinsed with a weakorganic acid, for example citric acid or tartaric acid. The hair is thendried.

[0043] The colorant of the invention containing a 3-aminophenolderivative of formula (I) as coupler gives colorations of excellentcolor stability, particularly in terms of light fastness, wash fastnessand rubbing fastness. As far as the coloring properties are concerned,depending on the kind and composition of the dye components, thecolorant of the invention provides a wide range of different colorshades ranging from blond to brown, purple, violet, blue and black. Saidshades are characterized by high color intensity. Furthermore, the verygood coloring properties of the colorant of the present patentapplication are, in particular, characterized by the fact that thiscolorant also makes it possible to dye gray, chemically not previouslydamaged hair with good covering power and without any problems.

[0044] The following examples are intended to illustrate the subjectmatter of the invention more closely without limiting its scope.

EXAMPLES Examples 1 to 6 Synthesis of 3-Aminophenol Derivatives ofGeneral Formula (I)

[0045] A. Synthesis of 2-bromo-3-nitrophenol

[0046] A solution of 10.5 g (152 mmol) of sodium nitrite in 40 mL ofwater was added slowly and dropwise to a suspension of 23.1 g (150 mmol)of 2-amino-3-nitrophenol in 40 ml of a 48% hydrobromic acid solution and12 mL of water at 0° C. The mixture was then allowed to agitate at 0° C.for 15 minutes. Subsequently, a suspension of 22.5 g of copper(I)bromide (Cu₂Br₂; 78.7 mmol) in 75 mL of a 48% hydrobromic acid solutionwas added dropwise, and the mixture was allowed to agitate at 0° C. for15 minutes and then at 100° C. for 1 hour. The reaction mixture was thencooled to about 5° C. and filtered, and the filter cake was washed witha small amount of water. This filter cake was then taken up with ethylacetate and filtered through silica gel. The solvent was then evaporatedto dryness under vacuum.

[0047] This gave 32.2 g. (98% of the theoretical) of2-bromo-3-nitrophenol. The crude product thus obtained was used in thenext step without additional purification.

[0048]¹H-NMR (300 MHz, CDCl₃): δ=7.47 ppm (dd, J=1.5 Hz/7.8 Hz, 1H, CH);7.37 ppm (t, J=8.1 Hz, 1H, CH); 7.26 ppm (dd, J=1.5 Hz/8.1 Hz, 1H, CH);6.08 ppm (s, 1H, OH).

[0049] EI-MS: 219/217 [M⁺] (40); 161/159 [M⁺-C—NO₂] (24)

[0050] B. Synthesis of 2-bromo-1-(methoxymethoxy)-3-nitrobenzene

[0051] 15 g (69 mmol) of 2-bromo-3-nitrophenol from step A was dissolvedin 150 mL of dry acetonitrile and to it was added portionwise at 0° C.3.5 g (117 mmol) of an 80% sodium hydride suspension. A solution of 6.1g (75 mmol) of chloromethoxymethane in 50 mL of dry acetonitrile wasthen added. At the end of the addition, the mixture was allowed toagitate overnight at room temperature. Ten mL of ethanol was added todecompose excess sodium hydride. The reaction mixture was then filtered,and the filtrate was evaporated to dryness in a rotary evaporator undervacuum. The crude product thus obtained was used in the next stepwithout further purification.

[0052] This gave 14.6 g (81% of the theoretical) of2-bromo-1-(methoxymethoxy)-3-nitrobenzene as a brown oil.

[0053]¹H-NMR (300 MHz. DMSO): δ=7.60-7.48 ppm (m, 3H, arom. —CH); 5.41ppm (s, 2H, CH₂); 3.44 ppm (s, 3H, CH₃).

[0054] MS (API-ES neg.): 218/216 [M−H]⁻ (100).

[0055] C. Synthesis of 3-aminophenols of Formula (I)

[0056] 0.26 g (1.0 mmol) of 2-bromo-1-(methoxymethoxy)-3-nitrobenzenefrom step B and 1.5 mmol of the corresponding boric acid derivative weredissolved in 5 mL of 1,2-dimethoxyethane under argon. Then, 0.18 g (0.15mmol) of tetrakis(triphenylphosphine)palladium(0) complex and 0.8 mL ofa 2N aqueous potassium carbonate solution were added, and the reactionmixture was heated to 100° C. At the end of the reaction, the reactionmixture was poured into 10 mL of ethyl acetate, the organic phase wasextracted with 5 mL of water and the aqueous phase was back-extractedtwice with ethyl acetate. The combined organic phases were then driedwith magnesium sulfate, and the solvent was distilled off in a rotaryevaporator. The residue was purified on silica gel using heptane/ethylacetate.

[0057] The product thus obtained was dissolved in 5 mL of ethanol andhydrogenated with gaseous hydrogen in the presence of about 50 mg ofpalladium (10% on active charcoal) at room temperature and normalpressure. At the end of the reaction, the reaction product was filteredthrough Cellite® and then concentrated. The resulting residue wastreated with 1 mL of a 2.9-molar ethanolic hydrochloric acid solution orwith 4-molar hydrochloric acid in dioxane. The reaction mixture wasallowed to agitate for about one hour at room temperature. At the end ofthe reaction, the precipitate was filtered off, washed with ethanol (ordioxane) and then dried. If no precipitation has occurred, the solventcan be evaporated in a rotary evaporator.

[0058] 1. 3-Amino-2-(3-thienyl)phenol hydrochloride

[0059] Boric acid derivative used: 3-thiophenylboric acid

[0060] Yield: 0.165 g (74% of the theoretical)

[0061]¹H-NMR (300 MHz, DMSO): δ=9.90 ppm (s, 1H, OH); 7.68-7.63 ppm (m,2H, arom. H); 7.23-7.17 ppm (m, 2H, arom. H); 6.88 ppm (t, J=6.9 Hz, 2H,arom. H); 3.8-3.3 ppm (br, NH₃ ⁺).

[0062] MS (API-ES pos.): 192 [M+H]⁺ (20).

[0063] 2. 3-Amino-2-(benzo[b]thiophen-3-yl)phenol hydrochloride

[0064] Boric acid derivative used: 1-benzothiophen-3-ylboric acid

[0065] Yield: 0.050 g (18% of the theoretical)

[0066] MS (API-ES pos.): 242 [M+H]⁺(50).

[0067] 3. 3-Amino-2-(2-thienyl)phenol hydrochloride

[0068] Boric acid derivative used: 2-thiophenylboric acid

[0069] Yield: 0.150 g (26% of the theoretical)

[0070]¹H-NMR (300 MHz. DMSO): δ=10.39 (s, 1H, OH); 6.43 ppm (d, J=4.41Hz, 1H); 6.13 ppm (t, J=1.7 Hz, J=8.17 Hz, 1H); 6.00 ppm (dd, J=3.6 and5.07 Hz, 1H); 5.89 ppm (d, J=2.6 Hz, 1H); 5.74 ppm (dd, J=8.4 and 10.7Hz, 2H); 3.7-3.3 ppm (s, br, NH₃ ⁺); 2.54 ppm (s, 3H, CH₃).

[0071] ESI-MS: 192 [M+1]⁺(85). CHN analysis: (C₁₀H₉NOS.HCl % C % H % N %Cl % S Calcd.: 52.75 4.43 6.15 15.57 14.08 Found: 52.50 4.40 6.10 15.5013.60

[0072] 4. 3-Amino-2-(benzo[b]thiophen-2-yl)phenol hydrochloride

[0073] Boric acid derivative used: 1-benzothiophen-2-ylboric acid

[0074] Yield: 0.008 g (14% of the theoretical)

[0075] MS (API-ES pos.): 242 [M+H]⁺(50).

[0076] 5. 3-Amino-2-(5-phenyl-2-thienyl)phenol hydrochloride

[0077] Boric acid derivative used: 5-phenyl-2-thienylboric acid

[0078] Yield: 0.048 g (16% of the theoretical)

[0079] MS (API-ES neg.): 266 [M−H]⁻ (100).

[0080] 6. 3-Amino-2-(3,5-dimethylisoxazol-4-yl)phenol hydrochloride

[0081] Boric acid derivative used: 3,5-dimethyl-4-isoxazolylboric acid

[0082] Yield: 0.070 g (30% of the theoretical)

[0083] MS (API-ES pos.): 227 [M+Na]⁺ (100).

Examples 7 to 12 Hair Colorants

[0084] Hair colorant solutions of the following composition wereprepared: 1.25 mmol of the substance of formula (I) as per Table 1 1.25mmol of the developer as per Table 1 10.0 g of lauryl ether sulfate (28%aqueous solution) 9.0 g of ammonia (22% aqueous solution) 7.8 g ofethanol 0.3 g of ascorbic acid 0.3 g of disodiumethylenediaminetetraacetate hydrate to 100.0 g water, demineralized

[0085] Just before use, 10 g of the above colorant solution was mixedwith 10 g of a 6% aqueous hydrogen peroxide solution. The mixture wasthen applied to bleached hair. After an exposure time of 30 minutes at40° C., the hair was rinsed with water, washed with a commercial shampooand dried. Table 1 summarizes the resulting colorations. TABLE 1Developer I II III IV V 4,5-diamino- 2,5-diamino- 1-(2′-hydroxy-2,4,5,6-tetra- Example Coupler of 2,5-diamino- phenylethanolethyl)pyrazole aminopyrimidine No. Formula (I) toluene sulfate sulfatesulfate 4-aminophenol sulfate 7 as per intense intense strawberryorange-brown gray Example 1 violet violet red 8 as per violetishvioletish strawberry weak orange gray Example 2 brown brown red 9 as perdark-bluish dark-bluish strawberry bright pink brown-green Example 3violet violet red 10 as per light — pink — — Example 4 brown 11 as perbrown brown red orange-brown brown-gray Example 5 12 as per violetishvioletish strawberry weak orange weak green Example 6 gray gray pink

Examples 13 to 24 Hair Colorants

[0086] Hair colorant solutions of the following composition wereprepared: X g of 3-aminophenol derivative of formula (I) (coupler K1 toK2 as per Table 4) U g of developer E8 to E15 as per Table 2 Y g ofcoupler K11 to K36 as per Table 4 10.0 g of lauryl ether sulfate (28%aqueous solution) 9.0 g of ammonia (22% aqueous solution) 7.8 g ofethanol 0.3 g of ascorbic acid 0.3 g of disodiumethylenediaminetetraacetate hydrate to 100.0 g water, demineralized

[0087] Just before use, 30 g of the above colorant solution was mixedwith 30 g of a 6% aqueous hydrogen peroxide solution. The mixture wasthen applied to bleached hair. After an exposure time of 30 minutes at40° C., the hair was rinsed with water, washed with a commercial shampooand dried. Tables 5 and 6 summarize the resulting colorations. TABLE 2Developers E8 1,4-diaminobenzene E9 2,5-diaminophenylethanol sulfate E103-methyl-4-aminophenol E11 4-amino-2-aminomethylphenol dihydrochlorideE13 N,N-bis-(2′-hydroxyethyl)-p-phenylenediamine sulfate E144,5-diamino-1-(2′-hydroxyethyl)pyrazole sulfate E15 2,5-diaminotoluenesulfate

[0088] TABLE 3 Direct Dyes D2 6-chloro-2-ethylamino-4-nitrophenol D32-amino-6-chloro-4-nitrophenol

[0089] TABLE 4 Couplers K1 3-amino-2-(3-thienyl)phenol K23-amino-2-(2-thienyl)phenol K12 2-amino-4-(2′-hydroxyethyl)aminoanisolesulfate K13 1,3-diamino-4-(2′-hydroxyethoxy)benzene sulfate K142,4-diamino-5-fluorotoluene sulfate K18 N-(3-dimethylamino)phenylureaK19 1,3-bis-(2,4-diaminophenoxy)propane tetrahydrochloride K213-aminophenol K22 5-amino-2-methylphenol K233-amino-2-chloro-6-methylphenol K24 5-amino-4-fluoro-2-methylphenolsulfate K25 1-naphthol K31 1,3-dihydroxybenzene K322-methyl-1,3-dihydroxybenzene K33 1-chloro-2,4-dihydroxybenzene K344-(2′-hydroxyethyl)amino-1,2-methylenedioxy- benzene.HCl K362-amino-5-methylphenol

[0090] TABLE 5 Hair Colorants Example No. 13 14 15 16 17 18 Dyes (Dyequantity in grams) K1 0.10 0.12 0.05 0.07 0.10 0.12 E8 0.30 E9 0.25 0.20E10 0.10 E15 0.25 0.30 0.25 K12 0.05 K13 0.05 K21 0.05 K22 0.05 K23 0.050.10 0.10 0.10 K25 0.10 K31 0.20 0.15 0.10 0.10 K32 0.20 0.10 K33 0.20K36 0.10 Coloring blond blond blond blond blond blond result

[0091] TABLE 6 Hair Colorants Example No. 19 20 21 22 23 24 Dyes (Dyequantity in grams) K2 0.10 0.12 0.05 0.07 0.10 0.12 E8 0.30 E9 0.25 0.20E10 0.10 E15 0.25 0.30 0.25 K12 0.05 K13 0.05 K21 0.05 K22 0.05 K23 0.050.10 0.10 0.10 K25 0.10 K31 0.20 0.15 0.10 0.10 K32 0.20 0.10 K33 0.20K36 0.10 Coloring blond blond blond blond blond blond result

Examples 25 to 30 Hair Colorants

[0092] Hair colorant solutions of the following composition wereprepared: X g of 3-aminophenol derivative of formula (I) (coupler K1 asper Table 4) U g of developer E8 to E15 as per Table 2 Y g of couplerK11 to K36 as per Table 4 Z g of direct dye D2 and D3 as per Table 310.0 g of lauryl ether sulfate (28% aqueous solution) 9.0 g of ammonia(22% aqueous solution) 7.8 g of ethanol 0.3 g of ascorbic acid 0.3 g ofdisodium ethylenediaminetetraacetate hydrate to 100.0 g water,demineralized

[0093] Just before use, 30 g of the above colorant cream[sic—Translator] was mixed with 30 g of a 6% aqueous hydrogen peroxidesolution. The mixture was then applied to hair. After an exposure timeof 30 minutes at 40° C., the hair was rinsed with water, washed with acommercial shampoo and dried. Table 7 summarizes the resultingcolorations. TABLE 7 Hair Colorants Example No. 25 26 27 28 29 30 Dyes(Dye quantity in grams) K1 0.60 1.30 1.15 0.15 0.15 0.15 E8 1.50 E110.10 E13 1.60 0.70 E14 0.10 0.10 E15 1.80 0.70 0.70 K12 0.50 K14 0.10K18 0.05 K19 0.10 K23 0.05 0.10 0.10 0.10 K24 0.15 K31 0.90 1.10 1.100.40 0.40 0.40 K34 0.10 D2 0.10 0.10 0.10 D3 0.05 0.05 0.05 Coloringblack black black brown brown brown result

[0094] Unless otherwise indicated, all percentages given in the presentpatent application are by weight.

1. 3-Aminophenol derivatives of formula (I) or the physiologicallycompatible, water-soluble salts thereof

wherein X₁, X₂, X₃ and X₄ independently of each other denote sulfur,nitrogen, N—R1, oxygen, C—R2, C—R3, C—R4 or C—R5, provided that at leastone and at the most three of the X₁ to X₄ groups denote nitrogen, N—R1,sulfur or oxygen and, if several heteroatoms are present, at the mostone of the X₁ to X₄ groups denotes sulfur, N—R1 or oxygen; R1 denoteshydrogen, a C₁-C₆-alkyl group, a phenyl group, a (C₂-C₄)-hydroxyalkylgroup or an acetyl group; R2, R3, R4 and R5 independently of each otherdenote hydrogen, a halogen atom, a cyano group, a C₁-C₄-alkyl group, aC₁-C₄-alkoxy group, a C₁-C₄-alkyl thioether group, a mercapto group, anitro group, an amino group, a C₁-C₄-alkylamino group, adi(C₁-C₄)-alkylamino group, a hydroxy-(C₂-C₄)-alkylamino group, adi[hydroxy-(C₂-C₄)alkyl]amino group, a [dihydroxy-(c3-C₄)-alkyl]aminogroup, a trifluoromethyl group, an acetyl group, a trifluoroacetylgroup, a formyl group, a trimethylsilyl group, a (C₁-C₄)hydroxyalkylgroup or a (C₂-C₄)-dihydroxyalkyl group, or two adjacent R2 to R5 groupstogether with the remainder of the molecule form an annelatedheterocyclic or carbocyclic, substituted or unsubstituted ring. 2.3-Aminophenol derivative according to claim 1, characterized in that itis selected from among 3-amino-2-(3-thienyl)phenol,3-amino-2-(3-furyl)phenol, 3-amino-2-(pyrrol-3-yl)phenol,3-amino-2-(1-methyl-1H-pyrrol-3-yl)phenol,3-amino-2-(1,3-thiazol-2-yl)phenol, 3-amino-2-(1,3-thiazol-5-yl)phenol,3-amino-2-(2-thienyl)phenol, 3-amino-2-(2-furyl)phenol,3-amino-2-(pyrrol-2-yl)phenol,3-amino-2-(1-methyl-1H-pyrrol-2-yl)phenol,3-amino-2-(2-chloro-3-thienyl)phenol,3-amino-2-(2-methyl-3-thienyl)phenol,3-amino-2-(benzo[b]thiophen-2-yl)phenol,3-amino-2-(5-phenyl-2-thienyl)phenol,3-amino-2-(2-nitro-3-thienyl)phenol,3-amino-2-(2-amino-3-thienyl)phenol,3-amino-2-(2-acetyl-3-thienyl)phenol,3-amino-2-(2-formyl-3-thienyl)phenol,3-amino-2-(4-chloro-3-thienyl)phenol,3-amino-2-(4-methyl-3-thienyl)phenol,3-amino-2-(4-nitro-3-thienyl)phenol,3-amino-2-(4-amino-3-thienyl)phenol,3-amino-2-(4-acetyl-3-thienyl)phenol,3-amino-2-(4-formyl-3-thienyl)phenol,3-amino-2-(5-chloro-3-thienyl)phenol,3-amino-2-(5-methyl-3-thienyl)phenol,3-amino-2-(5-phenyl-3-thienyl)phenol,3-amino-2-(5-nitro-3-thienyl)phenol,3-amino-2-(5-acetyl-3-thienyl)phenol,3-amino-2-(5-amino-3-thienyl)phenol,3-amino-2-(5-formyl-3-thienyl)phenol,3-amino-2-(benzo[b]thiophen-3-yl)phenol,3-amino-2-(5-formyl-3-furyl)phenol,3-amino-2-(3-chloro-2-thienyl)phenol,3-amino-2-(3-methyl-2-thienyl)phenol,3-amino-2-(3-nitro-2-thienyl)phenol,3-amino-2-(3-amino-2-thienyl)-phenol,3-amino-2-(3-acetyl-2-thienyl)phenol,3-amino-2-(3-formyl-2-thienyl)phenol,3-amino-2-(4-chloro-2-thienyl)phenol,3-amino-2-(4-methyl-2-thienyl)phenol,3-amino-2-(4-nitro-2-thienyl)phenol,3-amino-2-(4-amino-2-thienyl)phenol,3-amino-2-(4-acetyl-2-thienyl)phenol,3-amino-2-(4-formyl-2-thienyl)phenol,3-amino-2-(5-chloro-2-thienyl)phenol,3-amino-2-(5-methyl-2-thienyl)phenol,3-amino-2-(5-nitro-2-thienyl)phenol,3-amino-2-(5-amino-2-thienyl)phenol,3-amino-2-(5-acetyl-2-thienyl)phenol,3-amino-2-(5-formyl-2-thienyl)phenol,3-amino-2-(5-formyl-2-furyl)phenol,3-amino-2-(5-nitro-1,3-thiazol-2-yl)phenol,3-amino-2-(5-amino-1,3-thiazol-2-yl)phenol,3-amino-2-(2-nitro-1,3-thiazol-5-yl)phenol,3-amino-2-(2-amino-1,3-thiazol-5-yl)phenol,3-amino-2-(3,5-dimethylisoxazol-4-yl)phenol,3-amino-2-(3,5-dimethyl-1H-pyrazol-4-yl)phenol and3-amino-2-(5-nitro-4H-1,2,4-triazol-3-yl)phenol as well as thephysiologically compatible, water-soluble salts thereof. 3.3-Aminophenol derivative according to claim 1, characterized in that informula (I): (i) X₂ denotes sulfur and X₁, X₃ and X₄ denote C—R2, C—R4and C—R5 or (ii) X₁ denotes sulfur and X₂, X₃ and X₄ denote C—R3, C—R4and C—R5.
 4. 3-Aminophenol derivative according to one of claims 1through 3, characterized in that it is selected from among3-amino-2-(3-thienyl)phenol, 3-amino-2-(2-thienyl)phenol,3-amino-2-(benzo[b]thiophen-3-yl)phenol and3-amino-2-(5-phenyl-2-thienyl)phenol and the physiologically compatible,water-soluble salts thereof.
 5. Agent for coloring keratin fibers basedon a developer-coupler combination, characterized in that it contains asthe coupler at least one 3-aminophenol derivative of formula (I)according to one of claims 1 through
 4. 6. Agent according to claim 5,characterized in that it contains the 3-amino derivative of formula (I)in an amount from 0.005 to 20 weight percent.
 7. Agent according toclaim 5 or 6, characterized in that the developer is selected from thegroup consisting of 1,4-diaminobenzene, 1,4-diamino-2-methylbenzene,1,4-diamino-2,6-dimethylbenzene, 1,4-diamino-3,5-diethylbenzene,1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,3-dimethylbenzene,2-chloro-1,4-diaminobenzene, 1,4-diamino-2-(2-thienyl)benzene,1,4-diamino-2-(3-thienyl)benzene, 1,4-diamino-2-(pyridin-3-yl)benzene,2,5-diaminobiphenyl, 1,4-diamino-2-methoxymethylbenzene,1,4-diamino-2-aminomethylbenzene, 1,4-diamino-2-hydroxymethylbenzene,1,4-diamino-2-(2-hydroxyethoxy)benzene,2-[2-(acetylamino)ethoxy]-1,4-diaminobenzene, 4-phenylaminoaniline,4-dimethylaminoaniline, 4-diethylaminoaniline, 4-dipropylaminoaniline,4-[ethyl-(2-hydroxyethyl)amino]aniline,4-[di(2-hydroxyethyl)amino]aniline,4-[di(2-hydroxyethyl)amino]-2-methylaniline,4-[(2-methoxyethyl)amino]aniline, 4-[(3-hydroxypropyl)amino]aniline,4-[(2,3-dihydroxypropyl)amino]aniline,1,4-diamino-2-(1-hydroxyethyl)benzene,1,4-diamino-2-(2-hydroxyethyl)benzene,1,4-diamino-2-(1-methylethyl)benzene,1,3-bis-[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol,1,4-bis-[(4-aminophenyl)amino]butane,1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-aminophenol,4-amino-3-methylphenol, 4-amino-3-(hydroxymethyl)phenol,4-amino-3-fluorophenol, 4-methylaminophenol,4-amino-2-(aminomethyl)phenol, 4-amino-2-(hydroxymethyl)phenol,4-amino-2-fluorophenol, 4-amino-2-[(2-hydroxyethyl)amino]-methylphenol,4-amino-2-methylphenol, 4-amino-2-(methoxymethyl)phenol,4-amino-2-(2-hydroxyethyl)phenol, 5-aminosalicylic acid,2,5-diaminopyridine, 2,4,5,6-tetraminopyrimidine,2,5,6-triamino-4-(1H)-pyrimidone,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole,4,5-diamino-1-(1-methylethyl)-1H-pyrazole,4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole,1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole,4,5-diamino-1-methyl-1H-pyrazole, 2-aminophenol, 2-amino-6-methylphenol,2-amino-5-methylphenol and 1,2,4-trihydroxybenzene.
 8. Agent accordingto one of claims 5 to 7, characterized in that in addition to thecompounds of formula (I) it contains at least one other known couplerselected from the group consisting of N-(3-dimethylaminophenyl)urea,2,6-diaminopyridine, 2-amino-4-[(2-hydroxyethyl)amino]anisole,2,4-diamino-1-fluoro-5-methylbenzene,2,4-diamino-1-methoxy-5-methylbenzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene,2,3-diamino-6-methoxypyridine,3-amino-6-methoxy-2-(methylamino)pyridine,2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)benzene,1,3-diamino-4-(2,3-dihydroxypropoxy)benzene,1,3-diamino-4-(3-hydroxypropoxy)benzene,1,3-diamino-4-(2-methoxyethoxy)benzene,2,4-diamino-1,5-di(2-hydroxyethoxy)benzene,1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene,2,4-diaminophenoxyacetic acid, 3-[di(2-hydroxyethyl)amino]aniline,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene,5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline,3-[(2-aminoethyl)amino]aniline, 1,3-di(2,4-diaminophenoxy)propane,di(2,4-diaminophenoxy)methane, 1,3-diamino-2,4-dimethoxybenzene,2,6-bis-(2-hydroxyethyl)aminotoluene, 4-hydroxyindole,3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol,5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol,5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol,3-amino-2-chloro-6-methylphenol, 3-aminophenol,2-[(3-hydroxyphenyl)amino]acetamide,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,5-[(2-hydroxyethyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]phenol, 3-[(2-methoxyethyl)amino]phenol,5-amino-2-ethylphenol, 5-amino-2-methoxyphenol,2-(4-amino-2-hydroxyphenoxy)ethanol,5-[(3-hydroxypropyl)amino]-2-methylphenol,3-[(2,3-dihydroxypropyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 5-amino-4-chloro-2-methylphenol,1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 2-methyl-1-naphthol acetate,1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene,2-chloro-1,3-dihydroxybenzene,1,2-dichloro-3,5-dihydroxy-4-methylbenzene,1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline,5-[(2-hydroxyethyl)amino]-1,3-benzodioxole,6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)benzoxazine,6-amino-3,4-dihydro-1,4(2H)benzoxazine, 3-methyl-1-phenyl-5-pyrazolone,5,6-dihydroxyindole, 5,6-dihydroxyindoline, 5-hydroxyindole,6-hydroxyindole, 7-hydroxyindole and 2,3-indolinedione.
 9. Agentaccording to one of claims 5 through 8, characterized in that, based onthe total amount of colorant, the developers and couplers are present ina total amount from 0.005 to 20 weight percent, each.
 10. Agentaccording to one of claims 5 through 9, characterized in that itadditionally contains at least one direct dye.
 11. Agent according toone of claims 5 through 10, characterized in that it has a pH from 6.5to 11.5.
 12. Ready-for-use agent for oxidative dyeing of keratin fiberswhich, in a medium appropriate for dyeing, contains at least onedeveloper and at least one coupler as well as at least one oxidant,characterized in that it contains as the coupler at least one3-aminophenol derivative of formula (I) according to one of claims 1through
 4. 13. Agent according to one of claims 5 through 12,characterized in that it is a hair colorant.
 14. Method for oxidativedyeing of hair, particularly human hair, characterized in that, beforeuse, a hair colorant according to one of claims 5 through 13 is mixedwith an oxidant, applied to the hair and allowed to act on the hair at atemperature from 15 to 50° C. for 10 to 45 minutes, after which the hairis rinsed with water, optionally washed with a shampoo and then dried.